Preparation of phenylphenol dyeing assistant compositions



United States Patent PREPARATION OF PHENYLPHENOL DYEING ASSISTANT COMPOSITIONS Harlan B. Freyermnth and Charles L. Lawsberg, Easton, Pa., assignors to General Aniline & Film Corporation, New York, N. a corporation of Delaware No Drawing. Application April 30, 1956 Serial No. 581,309

4 Claims. or. 8-93) v 2,926,987 Patented Mar. 1, 1.960

structure of water-impermeable polymeric materials a dispersed powder of orthophenylphenol or paraphenylphenol which is prepared by working a mixture of the phenylphenol anda suitable dispersing agent in a dispersion mill in the presence of a small quantity of water, drying the resultant powder at an elevated temperature until substantially all of the water is removed, and grinding the dry powder to greater fineness in. a hammer mill.

Any suitable anionic dispersing agent may be employed in the preparation of the dispersed powder of orthophenylphenol or paraphenylphenol such as, for example, sodium salts of naphthalene sulfonic acid-formaldehyde condensation products (Tamol NNO), sodium terials which are not readily permeable to water such as,

for example, the polyesters of terephthalic acid and ethylene glycol, the polymers of acrylonitrile, the copolymers of acrylonitrile and vinyl chloride, the vinyl resins, the cellulose acetates and nylon, which materials will hereinafter be designated as water-impermeable polymeric materials.

It is well known in the art of dyeing that when it is attempted to dye textile structures of water-impermeable polymeric materials by the dyeing procedures ordinarily used in dyeing textile structures of cotton, silk, wool and regenerated cellulose, the dyestuft either does not penetrate the water-impermeable polymeric materials thus effecting no coloration on said materials, or when a coloration is efiected it is fugitive and leaches out during a washing step. It is also well known in the dyeing art that the dyeing of textile structures of water-impermeable polymeric materials may be improved by the use in the dyebath of dyeing assistants which may function as imbibing agents, swelling agents or carriers.

Among the dyeing assistants heretofore employed in the dyeing of textile structures of water-impermeable polymeric materials with acid and acetate dyestuiis are the phenylphenols, substituted and unsubstituted. The most useful of the phenylphenols and therefore most widely employed as a dyeing assistant in the dyeing of water-impermeable polymeric materials are orthophenylphenol and paraphenylphenol. However, in the, prior processes using these dyeing assistants, it was necessary to predissolve said phenylphenols in a caustic solution and then to release the phenylphenol in the presence of t a dispersing agent by the addition to-said solutionrof acetic acid.

It is an important object of this invention to provide an improved process for dyeing textile structures of water-impermeable polymeric materials wherein the necessity of first forming the sodium salt of the phenylphenol and then regenerating the phenylphenol by the addition of an acid is eliminated.

Another object of this invention is the provision of a novel dyeing assistant composition containing. orthophenylphenol or paraphenylphenol for use in the dyeing of textile structures of water-impermeable polymeric ma terials.

A further object of this invention is the provision of a novel process for the preparation of the orthophenyl- ".f

phenol or paraphenylphenol dyeing assistant composition. Other objects and advantages of this invention will appear in the following detailed description and appended claims.

=.-.=In accordance with the instant invention, there is employed as a dyeing assistant in the dyeing of textile lignin sulfonates (Marasperse B and N), sodium salts of partially desulfonated lignin sulfonic acids (Marasperse CB), and secondary licorice extracts (Flotite). It is preferred, however, to use the sodium lignin sulfonate dispersing agents since they are not only eitective surfactants but they are also relatively inexpensive. The amount of dispersing agent necessary to disperse the paraphenylphenol may vary from 25% to The dyeing of-the textile structures is effected in accordance with this invention by first forming a paste of the acid or acetate dyestufi and the dispersed powder of orthophenylphenol or paraphenylphenol. A dyebath is then formed from the paste in a dye vessel, and the textile structure is entered into the dyebath. The temperature of the contents of, the dyevessel is raised to the boil and maintained at,the boil for the required length of time after which the dyed textile structure is rinsed in cold water and dried.

The instant invention will be understood more clearly from the illustrative examples. Parts, proportions and percentages are by weight unless otherwise indicated.

Example I Ten parts of paraphenylphenol and 10 parts of Tamol NNO were placed in a Werner Pflciderer type dispersion mill. Ten parts of water were added and the material was milled in a viscous state for two and one-half hours. Steam was passed through the jacket to remove part of the water to increase the viscosity of the mix during the first 15-20 minutes. The steam was then shut ofi. At the end of the milling period the heat of friction of milling removed most of the water and a powder was finally obtained. The powder was thoroughly dried in an oven at 55 C. overnight. The powder was then ground in a hammer mill.

Example II The procedure of Example I was followed except that 10 parts of Marasperse CB were used in place of 10 parts of Tamol NNO.

I Example III 0.3 part Celliton .Blue G Extra, 1,4,5,8-tetraaminoanthraquinone,

H1111 1? NH:

contents of the dye vessel was raised to the boil in 15-20 minutes, with continual manipulation of the goods. The fabric was dyed at the boil for one and one-half hours after which time it was rinsed in cold water and dried. The fabric was dyed a level blue shade. 7

Example IV 0.3 part of Celliton Fast Yellow 4RL Conc., benzeneazo-benzene-azo-phenol,

was pasted with 2 parts Igepon T and 50 parts warm 120 F.) water were added. 0.6 part paraphenylphenol dispersed with 50% Tamol NNO was treated separately with 50 parts warm (120 F.) water and after stirring a few minutes, the dispersed dye solution was added. 200 parts of cold water were then added. 10 parts of boiled off fabric of polyester of terephthalic acid and ethylene glycol were entered into the dye bath and the temperature was raised to the boil. The fabric was dyed at the boil for one and one-half hours and then rinsed and dried. The fabric was dyed a level orange shade.

Example V The procedure of Example III was followed except that 0.3 part of CellitonFast Blue FFRS,

I NH R R=CH and C H.;OH mixture was used in place of 0.3 part Celliton Blue G Extra. A level dyeing resulted and the fabric was dyed a deep, bright blue shade.

Example VI The procedure of Example V was followed except that 0.6 part of paraphenylphenol dispersed with 50% Marasperse CB was used instead of 0.6 part of paraphenylphenol dispersed with 50% Tamol NNO. The fabric was dyed a bright blue shade and a level dyeing was obtained.

Example Vll moan V Color Index No. 228, all previously and separately dissolved in water. Enough water was added to make a total of about 300 parts and the temperature was raised "to the boil for one and one-half hours with continued stirring. The dyed goods was rinsed in cold water and dried. A'level dyeing resulted and the fabric was dyed a deep bright blue shade.

4 Example VIII Ten parts of orthophenylphenol and ten parts of Tamol NNO were placed in a Werner Pfleiderer type dispersion mill. Five parts water were added and the material was milled in a viscous state for two and one half hours. Cold water was run through the jacket'of the mill to keep the temperature of the mix below the melting point (56 C.) of the orthophenylphenol. The milled material was dried in a vacuum oven at 50 C. The product was ground in a hammer mill.

Example IX The process in Example III was followed except that 0.6 part of a 50% dispersion of orthophenylphenol was used in place of 0.6 part of paraphenylphenol.

Example X The process in Example VII was followed except that 0.6 part of a 50% dispersion of orthophenylphenol was used in place of 0.6 part paraphenylphenol.

The dyeing process of the instant invention has many advantages over the dyeing processes of the prior art where dyeing assistants such as the phenylphenols are employed. Thus, it is much more convenient to the dyer to use dispersed powder of paraphenylphenol as it eliminates the necessity of first forming the sodium salt and then regenerating the phenol by addition of an acid. The possibilities of errors are minimized and the desired pH of the dyebath is more easily maintained. This is particularly important if acetate dyes are used. It is also a convenience and advantage to the dyer to add the dyestuif and the dispersed dyeing assistant simultaneously than to have to pretreat the textile structure to be dyed with paraphenylphenol as has been found necessary heretofore.

It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.

Having described our invention what we desire to secure by Letters Patent is:

1. In a process for dyeing a textile structure wherein the dyeing medium comprises a dyestuff for the material of the textile structure and a dyeing assistant composition, the improvement which comprises the use, in cornbiuation with the dyestuif, of a dyeing assistant composition consisting essentially of a dispersed powder prepared by milling a mixture of a phenylphenol selected from the group consisting of orthophenylphenol and paraphenylphenol, an anionic dispersing agent and Water in a viscous state, passing steam through said mixture during the milling thereof to remove part of said water, continuing the milling of said mixture until a dry powder is obtained, subjecting said dry powder to the action of heat, and then grinding said powder to greater fineness.

2. In a process for dyeing a textile structure wherein the dyeing medium comprises a dyestuif for the material of the textile structure and a dyeing assistant composition, the improvement which comprises the use, in combination with the dyestuif, of a dyeing assistant composition consisting essentially of a dispersed powder prepared by milling a mixture of a phenylphenol selected from the group consisting of orthophenylphenol and paraphenylphenol, a sodium lignin sulfonate dispersing agent and water in a viscous state, passing steam through said mixture during the milling thereof to remove part of said Water, continuing the milling of said mixture until a dry powder is obtained, subjecting said dry power to the action of heat, and then grinding said powder to greater fineness.

3. In a process for dyeing a textile structure wherein the dyeing medium comprises a dyestuff for the material of the textile structure and a dyeing assistant composition, the improvement which comprises the use, in combinationwith the dyestufi, of a dyeing assistant composition consisting essentially of a dispersed powder prepared by milling a mixture or" a phenylphenol selected from the group consisting of orthophenylphenol and paraphenylphenol, a sodium lignin sulfona'te dispersing agent and water, in a viscous state, passing steam through stid mixture during the milling thereof to remove part of said water, continuing the milling of said mixture, until adry powder is obtained, subjecting said dry powder to the action of heat, and then grinding said powder to greater fineness.

4. In a process for dyeing a textile structure wherein the dyeing medium comprises a dyestuif for the .materiai of the textile structure and a dyeingassistant composition, the improvement which comprises the use, in combination with the dyestufi, of a dyeing assistant composition consisting essentially of a dispersed powder prepared by milling a mixture of a phenylphenol selected from the group consisting of orthophenylphenol and para- References Cited in the file of this patent UNITED STATES PATENTS 2,394,688 Heyman Feb. 12; 1946 2,734,793 Marnon Feb. 14, 1956 FOREIGN PATENTS 505,940 Canada Sept. 21, 1954 701,814 Great Britain Jan. 6, 1954 

1. IN A PROCESS FOR DYEING A TEXTILE STRUCTURE WHEREIN THE DYEING MEDIUM COMPRESES A DYESTUFF FOR THE MATERIAL OF THE TEXTILE STRUCTURE AND A DYEING ASSISTANT COMPOSITION, THE IMPROVEMENT WHICH COMPRISES THE USE, IN COMBINATION WITH THE DYESTUFF, OF A DYEING ASSISTANT COMPOSITION CONSISTING ESSENTIALLY OF A DISPERSED POWDER PREPARED BY MILLING A MIXTURE OF A PHENYLPHENOL SELECTED FROM THE GROUP CONSISTING OF ORTHOPHENYLPHENOL AND PARAPHENYLPHENOL, AND ANIONIC DISPERSING AGENT AND WATER IN A VISCOUS STATE, PASSING STEAM THROUGH SAID MIXTURE DURING THE MILLING THEREOF TO REMOVE PART OF SAID WATER, CONTINUING THE MILLING OF SAID MIXTURE UNTIL A DRY POWDER IS OBTAINED, SUBJECTING SAID DRY POWDER TO THE ACTION OF HEAT, AND THEN GRINDING SAID POWDER TO GREATER FINENESS, 